Characterization and Electrophoretic Deposition of Poly(Phenylsilsesquioxane)–Titania Hybrid Particles Prepared by the Sol–Gel Method

Poly(phenylsilsesquioxane)–titania (PhSiO_3/2–TiO₂) hybrid particles were prepared from phenyltriethoxysilane and titanium tetra- n -butoxide by the sol–gel method. Fourier transform infrared spectra showed that PhSiO_3/2 and the TiO₂ components were hybridized through Si–O–Ti bonds. The refractive index of the particles was monotonically increased from 1.57 to 1.62 with an increase in the TiO₂ content. The PhSiO_3/2–TiO₂ particles were electrophoretically deposited on indium tin oxide (ITO)-coated glass substrates to form opaque, thick films about 3 μm in thickness. When the mole ratio x in (1− x )PhSiO_3/2· x TiO₂ was equal to or less than 0.05, the deposited PhSiO_3/2–TiO₂ films became transparent with a heat treatment at 400°C because of the thermal sintering of the particles.     

Micropatterning of Transparent Poly(Benzylsilsesquioxane) Thick Films Prepared by the Electrophoretic Sol–Gel Deposition Process Using a Hydrophobic–Hydrophilic-Patterned Surface

Poly(benzylsilsesquioxane) (BnSiO_3/2) particles show glass transition behavior, and the particles become a supercooled liquid when they are heated at temperatures above the glass transition temperature. Contact angles of BnSiO_3/2 molten liquid on the hydrophobic surface with fluoroalkylsilane and hydrophilic surface with silica were found to be around 77° and 12°, respectively. Using the difference in wettability for BnSiO_3/2 molten liquid between the hydrophobic and hydrophilic surfaces, micropatterns of transparent BnSiO_3/2-thick films were formed by the electrophoretic deposition of BnSiO_3/2 particles on indium tin oxide substrates with hydrophobic–hydrophilic patterns and subsequent heating above the glass transition temperature.     

Sol–Gel Synthesis and Characterization of Ag and Au Nanoparticles in SiO2, TiO2, and ZrO2 Thin Films

Silver and gold nanoparticles were synthesized by the sol–gel process in SiO₂, TiO₂, and ZrO₂ thin films. A versatile method, based on the use of coordination chemistry, is presented for stabilizing Ag⁺ and Au³⁺ ions in sol–gel systems. Various ligands of the metal ions were tested, and for each system it was possible to find a suitable ligand capable of stabilizing the metal ions and preventing gold precipitation onto the film surface. Thin films were prepared by spin-coating onto glass or fused silica substrates and then heat-treated at various temperatures in air or H₂ atmosphere for nucleating the metal nanoparticles. The Ag particle size was about 10 nm after heating the SiO₂ film at 600°C and the TiO₂ and ZrO₂ films at 500°C. After heat treatment at 500°C, the Au particle size was 13 and 17 nm in the TiO₂ and ZrO₂ films, respectively. The films were characterized by UV–vis optical absorption spectroscopy and X-ray diffraction, for studying the nucleation and the growth of the metal nanoparticles. The results are discussed with regard to the embedding matrix, the temperature, and the atmosphere of the heat treatment, and it is concluded that crystallization of TiO₂ and ZrO₂ films may hinder the growth of Ag and Au particles.     

Fabrication and Properties of Sol–Gel-Derived BiScO3–PbTiO3 Thin Films

BiScO₃–PbTiO₃ (BSPT) thin films near the morphotropic phase boundary were successfully fabricated on Pt(111)/Ti/SiO₂/Si substrates via an aqueous sol–gel method. The thin films exhibited good crystalline quality and dense, uniform microstructures with an average grain size of 50 nm. The dielectric, ferroelectric, and piezoelectric properties of the sol–gel-derived BSPT thin films were investigated. A remanent polarization of 74 μC/cm² and a coercive field of 177 kV/cm were obtained. The local effective piezoelectric coefficient d ^*₃₃ was 23 pC/N at 2 V, measured by a scanning probe microscopy system. The dielectric peak appeared at 435°C, which was 80°C higher than that of Pb(Ti, Zr)O₃ thin films.     

Nanometer-Sized ZrO2 Particles Prepared by a Sol–Emulsion–Gel Method

ZrO₂ powder was prepared by a sol–emulsion–gel method at temperatures below 140°C from ZrO(NO₃)₂· n H₂O. The asprepared powder was amorphous, but crystallized into the tetragonal structure by 600°C. The metastable tetragonal powder (600°C) was comprised of ultrafine 4- to 6-nm size particles. On heat treatment, the tetragonal form completely transformed into the monoclinic state at 1100°C. Preliminary studies indicate good sinterability with densities greater than 94% at 1100°C and with a grain size of 0.25 μ.     

Properties of Lead Zirconate Titanate Thin Films Prepared Using a Triol Sol–Gel Route

Microstructure and phase development during the thermal decomposition of sol–gel precursor coatings of PbZr_0.53Ti_0.47O₃ on platinized silicon substrates have been investigated for a triol sol–gel route. The single-layer, 0.4 μm PZT films were heated from below the substrate, over the temperature range 350–600°C, using a calibrated hot plate. The first crystalline phase to appear was a PbPt₃ intermetallic phase at the Pt/PZT interface. Although perovskite PZT formed at ca. 500°C, heating at higher temperatures, for example 550°C for 30 min, was required to develop ferroelectric hysteresis loops. However, the rather low value of remanent polarization, P _r= 11 μC·cm⁻², was consistent with incomplete crystallization at 550°C. The values of remanent polarization increased with increasing processing temperatures, reaching 21 μC·cm⁻² for samples heated at 600°C, with a corresponding E _c value of 57 kV·cm⁻¹. Distinctive spherical precipitates up to ca. 50 nm in size have been identified by TEM in the lower portions of otherwise amorphous coatings, after heating at around 350–400°C. Although their precise composition could not be identified, they were mostly Pb-rich, and it is speculated that they form due to reduction of some of the lead(II) acetate starting reagent, to atomic Pb during the early stages of thermal decomposition of the organic components of the gel; it is possible that subsequent reactions occur to form lead oxides or carbonates. High levels of porosity were present in many of the fully crystallized films. The possible reasons for this are discussed.     

(Na0.8K0.2)0.5Bi0.5TiO3 Nanowires: Low-Temperature Sol–Gel–Hydrothermal Synthesis and Densification

The sol–gel–hydrothermal processing of (Na_0.8K_0.2)_0.5Bi_0.5TiO₃ (NKBT) nanowires as well as their densification behavior were investigated. The morphology and structure analyses indicated that the sol–gel–hydrothermal route led to the formation of phase-pure perovskite NKBT nanowires with diameters of 50–80 nm and lengths of 1.5–2 μm, and the processing temperature was as low as 160°C, but the conventional sol–gel route tended to lead to the formation of NKBT agglomerated porous structured nanopowders, and the processing temperature was higher than 650°C. It is believed that the gel precursor and hydrothermal environment play an important role in the formation of the nanowires at a low temperature. Owing to the better packing efficiency and therefore a good sinterability of the freestanding nanowhiskers, the pressed pellets made by NKBT nanowires showed >98% theoretical density at 1100°C for 2 h. The sol–gel–hydrothermal-derived ceramics have typical characteristics of relaxor ferroelectrics, and the piezoelectric properties were better than the ceramics prepared by the conventional sol–gel and solid-state reaction.     

Preparation of CuAlO2 Films by Wet Chemical Synthesis

CuAlO₂ is a delafossite-type compound and is a known p -type semiconductor. Transparent CuAlO₂ thin films were prepared using a sol–gel technique. The films with an Al/Cu atomic ratio of 1.0 consisted of CuAlO₂, Cu₂O, and CuO after heat treatment at 800°–900°C in nitrogen gas. The electrical resistivity of the film heated at 800°C was 250 Ω·cm.     

Synthesis of Nd:YVO4 Thin Films by a Sol-Gel Method

Nd: YVO₄ powders and thin films were successfuly synthesized by the sol–gel method using metal alkoxides. A homogeneous and stable solution was prepared by the reaction of Y(OEt)₃, VO(O i Pr)₃, and Nd(OEt)₃ in 2-methoxyethanol. The precursor was a mixture of vanadium and yttrium double alkoxide. Precursor films were prepared by dip coating and crystallization to single-phase YVO₄ at 500°C. Nd:YVO₄ films were crystallized with (200) preferred orientation on glass substrates, which showed the characteristic optical absorption of neodymium.     

Dielectric and Piezoelectric Properties of PZT Composite Thick Films with Variable Solution to Powder Ratios

The use of PZT films in sliver-mode high-frequency ultrasonic transducers applications requires thick, dense, and crack-free films with excellent piezoelectric and dielectric properties. In this work, PZT composite solutions were used to deposit PZT films >10 μm in thickness. It was found that the functional properties depend strongly on the mass ratio of PZT sol–gel solution to PZT powder in the composite solution. Both the remanent polarization, P _r, and transverse piezoelectric coefficient, e _{31, f} , increase with increasing proportion of the sol–gel solution in the precursor. Films prepared using a solution-to-powder mass ratio of 0.5 have a remanent polarization of 8 μC/cm², a dielectric constant of 450 (at 1 kHz), and e _{31, f} =−2.8 C/m². Increasing the solution-to-powder mass ratio to 6, the films were found to have remanent polarizations as large as 37 μC/cm², a dielectric constant of 1250 (at 1 kHz) and e _{31, f} =−5.8 C/m².     

(100)-Orientation of Pseudocubic Perovskite-Type LaNiO3 Thin Films on Glass Substrates via the Sol–Gel Process

(100)-oriented, perovskite-type LaNiO₃ thin films were prepared on SiO₂ glass substrates by the sol–gel method. Effects of thermal processing on the orientation, surface morphology, and electrical properties of the films were investigated. The nearly complete (100)-orientation was achieved by drying the films at temperatures above 350°C before a final heat treatment at 700°C. It was the key to heat the substrate from the other side to obtain the oriented films. A possible mechanism of the orientation is proposed on the basis of surface energies of the films and the substrates and the interfacial energy between them.     

Low Temperature Preparation of Ferroelectric Relaxor Composite Thick Films

In this work, the fabrication and characterization of a composite films comprising classical ferroelectric (PbTiO₃, PT) and relaxor (PbMg_1/3Nb_2/3O₃, PMN) material is reported. Thick films consisting of ferroelectric and relaxor phases in the thickness range of 2–10 μm are fabricated on Pt-coated Si substrates at a temperature of ≤550°C via a modified sol–gel route. The phase purity of the composite films was determined by X-ray powder diffraction pattern. The morphology and composition homogeneity were analyzed by scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), and by X-ray mapping method, respectively. High dielectric permittivity (ɛ≈1100) and low loss values (tan δ≈0.03) at 1 kHz and room temperature were measured on 2-μm-thick composite films for a particular composition of 83 mol% of a PT phase and 17 mol% of a PMN phase, with associated remanent polarization of P ≈31.6 μC/cm² and coercive field of E _c ≅166 kV/cm. Piezo-response force microscopy analysis of the composite film showed that the film is piezoelectric and switchable. The temperature dependence of the effective dielectric permittivity and loss of the films at different frequencies was studied in the temperature range −50° to 200°C. In the temperature range used for applications (−50° to +100°C) the composite shows quite low temperature coefficient of capacitance (TCC=100%( C _T− C _−50°)/ C _−50°C))=18%, much lower than both PMN thick film and PT film in the same temperature range. This composition is therefore promising for low TCC applications.     

Preparation of β-BaB2O4 Powders and Thin Films by Sol–Gel Method

β-BaB₂O₄ (β-BBO) powders and films were successfully synthesized by the sol–gel method using metal alkoxides. A homogeneous and stable solution was prepared by the reaction of barium metal with boron triethoxide in ethanol by addition of diethanolamine. The drip-coated precursor films began to crystallize to β-BBO on Pt substrates at 500°C and converted to β-BBO films with preferred orientation to the c -axis at 700°C.     

Phase Separation in an SiCO Glass Studied by Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy

SiCO glasses prepared from sol–gel precursors via pyrolysis in argon at temperatures ranging from 1000° to 1400°C were studied by transmission electron microscopy (TEM), in conjunction with electron energy-loss spectroscopy (EELS). EELS analysis showed that stoichiometric SiCO glass underwent phase separation, forming SiO₂- and SiC-based environments. This process started at ∼1200°C. However, at temperatures >1300°C, precipitation of nanometer-sized SiC particles embedded in vitreous SiO₂ was monitored by high-resolution TEM.     

Sol–Gel Synthesis of λ–Na2O·xAl2O3 Films

Na₂O· x Al₂O₃ ( x = 9, 11)films have been obtained by sol–gel method. Crystallization processes during heat treatments have been investigated by X–ray diffraction analysis. A metastable phase with the mullite structure, λ–Na₂O· x Al₂O₃, has been observed starting from 800°C. Films remained stable after a heat treatment at 1000°C for 250 h. Impedance spectroscopy measurements showed that the films of λ-Na₂O· x Al₂O₃ possess a large three–dimensional ionic conductivity at 400°C.     

Synthesis and Stability of Nanocrystalline Lead Stannate

Nano-crystalline PbSnO₃ was synthesized by a sol–gel route. It was an anion-deficient pyrochlore ( a = b = c = 1.0677 nm) with space group Fd3m. TEM images confirmed the nano-size of particles as ∼10 nm, aggregated into larger clusters up to 1 μm. DSC-TGA investigation revealed that the PbSnO₃ was unstable >800°C with 2.95% weight loss. The products of the reactions, Pb₂SnO₄ and SnO₂, were identified by in situ high-temperature XRD. The complex decomposition reactions were deduced as (2 + x )PbSnO₃= Pb₂SnO₄+ (1 + x )SnO₂+ x PbO ( x = 0.104). The lattice parameters of PbSnO₃ were determined by high-temperature XRD. The cell volume of PbSnO₃ increased with increasing temperatures. The average volumetric thermal expansion of PbSnO₃ was calculated as (β= 3.35 × 10⁻⁵/°C).     

Synthesis of Perovskite-Type (La1−xSrx)MnO3 (O X 0.3) at Low Temperature

Perovskite-type (La_{1- x} Sr _x )MnO₃ (0 x 0.3) was synthesized through the sol–gel process at low temperature (400° to 500°C). Poly(acrylic acid) (PAA) was used to make a gel from an aqueous solution of lanthanum, strontium, and manganese nitrates. The particle-diameter distribution of the manganites had a maximum value of 0.3 to 0.7 μ m, and a specific surface area of about 17.5 to 23.5 m²/g.     

Fabrication of Lanthanum Manganese Oxide Thin Films on Yttria-Stabilized Zirconia Substrates by a Chemically Modified Alkoxide Method

Perovskite-type thin films of lanthanum manganese oxide (LaMnO₃) were prepared on yttria (8%) stabilized zirconia substrate by the sol–gel process from an alkoxide solution of lanthanum isopropoxide (La(O- i -C₃H₇)₃) and manganese isopropoxide (Mn(O- i -C₃H₇)₂). The alkoxide solution was chelated with 2-ethyacetoacetate, and further modified with polyethylene glycol (PEG). The obtained LaMnO₃ thin film was transparent and macroscopically crackless. X-ray diffraction, differential thermal analysis–thermogravimetry analysis, and scanning electron microscope observations indicated that single-phase LaMnO₃ thin films with a grain size of 80 to 100 nm are formed when a spin-coated LaMnO₃ gelled film is heated at 600°C for 1 h. The porous and homogeneous grain structure with a grain size of <100 nm can be obtained when the LaMnO₃ gelled film is heated at 600° and 800°C. It was considered that PEG might accelerate the crystallization of the perovskite phase, which indicates that PEG assists the formation of the La-O-Mn frame network during partial hydrolysis and condensation reactions in sol–gel processes.     

Microstructure of KTaxNb1−xO3 Thin Films on MgO (100) Single Crystals

Thin KTa_xNb_1−xO₃ (KTN) films were prepared by deposition of sol–gel precursor solutions on MgO (100) single crystals. Crystal structure and microstructure of the films as a function of processing parameters, such as rate, duration, and temperature of postdeposition heat treatment, were studied. Several techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were employed to analyze the films. It was observed that slow heating of KTN films promotes pyrochlore formation while fast-firing of the films results in predominant formation of the perovskioe phase. In slow-heated samples, TEM showed randomly oriented pyrochlore crystallites with a vermicular nanostructure of 10–30 nm with an interpenetrating porosity of the same range. In fast-fired samples, large perovskite pockets with pyrochlore crystallites scattered among them were seen. The large perovskite grains were on the order of 0.1–0.5 μm, irregular in shape and porous. Transmission electron diffraction indicated these were single crystals, and ferroelectric domains were observed in them. Films of up to 1 μm thick were obtained by multiple deposition of the sol–gel KTN. Dense films were achieved when each layer was densified at 750°C for 2 h before the next layer was deposited.     

Sol-Gel Preparation of Pb(Zr0.50Ti0.50)O3 Ferroelectric Thin Films Using Zirconium Oxynitrate as the Zirconium Source

Lead zirconium titanate (Pb(Zr_0.5Ti_0.5)O₃, PZT) ferroelectric thin films were successfully deposited on platinum-coated silicon substrates and platinum-coated silicon substrates with a PbTiO₃ interlayer by using a modified sol–gel spin-coating process, using zirconium oxynitrate dihydrate as the zirconium source. The precursor solution for spin coating was prepared from lead acetate trihydrate, zirconium oxynitrate dihydrate, and tetrabutyl titanate. The use of zirconium oxynitrate instead of the widely used zirconium alkoxide provided more stability to the PZT precursor solution and a well-crystallized structure of PZT film at a relatively low processing temperature. PZT films that were annealed at a temperature of 700°C for 2 min via a rapid thermal annealing process formed a well-crystallized perovskite phase of PZT films and also had nanoscale uniformity. The microstructure and morphology of the prepared PZT thin films were investigated via X-ray diffractometry, transmission electron microscopy, and atomic force microscopy techniques. The values for the remnant polarization ( P ) and coercive electric field ( E ) of the PZT films that were obtained from the P–E loop measurements were 3.67 μC/cm² and 54.5 kV/cm, respectively.